Abstract
A new two step oxidation model is proposed that describes the mechanism of internal oxidation of the non-noble impurities antimony and indium in silver. We have found that internal oxidation at 550 K leads to the formation of isolated SbO2 or InO2 molecules, respectively. The commonly used model of Wagner treats the oxidation as a one step process, which means that in the case of antimony and indium two oxygen atoms must be trapped effectively in one step. Assuming a trapping radius of one lattice constant this model predicts an oxidation front that is much steeper than observed experimentally. The two step oxidation model assumes that first one oxygen atom is trapped at the non-oxidized impurity to form a relatively unstable complex. If within the lifetime of this complex a second oxygen atom is trapped, a stable and completely oxidized complex is formed in the silver matrix. The two step oxidation model predicts the shape of the oxidation front during internal oxidation at 550 K of antimony or indium in silver single crystals correctly, when a dissociation energy of 0.60(5) eV for the unstable complex is taken.
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Segeth, W., Boerma, D.O., Niesen, L. et al. Mechanism of internal oxidation of Sb and in in silver. Z. Physik B - Condensed Matter 73, 43–48 (1988). https://doi.org/10.1007/BF01312153
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DOI: https://doi.org/10.1007/BF01312153